Efficient Metal-free Electrocatalyst Research Articles

Sulfur and nitrogen dual-doped graphdiyne as a highly efficient metal-free electrocatalyst for the Zn-air battery

Sulfur and nitrogen dual-doped graphdiyne as a highly efficient metal-free electrocatalyst for the Zn-air battery

Manganese doped tailored cobalt sulfide as an accelerated catalyst for oxygen evolution reaction

Developing an efficient, robust, and noble metal-free electrocatalyst that can catalyse oxygen evolution reactions (OER) remains a significant challenge. CoS2, a representative of pyrite form transition metal dichalcogenides, has recently been identified as an economical catalyst. Here, an incredibly quick and scalable technique for novel catalysts synthesized with the use of the microwave method was introduced. Manganese-doped cobalt sulphide (Mn-CoS2) showed outstanding OER with a very low overpotential of 227 mV at 10 mA cm−2. Exposure of surface atoms resulted in high electrochemical activity, where the defects facilitated charge and mass transfer along the nanostructure, allowing surface dependent electrochemical reactions to be performed more efficiently. The electronic properties of pristine and transition-metal-doped CoS2 structures were also investigated using density functional theory (DFT). To better understand transition metal’s dependent impact on crystal structure, orbital electronic participation, charge density, and charge transformation in both pristine and Mn-dopedCoS2 frameworks were calculated and analysized. Our synthesis approach is primarily commercial and extensible, overcoming synthesis challenge of transition metal sulphide nanostructures with prime quality and implying a potential for commercial uses.

Disentangling the catalytic origin in defect engineered 2D NiCoMoS@Ni(CN)2 core-shell heterostructure for energy-saving hydrazine-assisted water oxidation

The major hindrance to efficient electrocatalytic hydrogen generation from water electrolysis is the sluggish kinetics with corresponding large overvoltage of oxygen evolution reaction. Herein, we report a defective 2D NiCoMoS@Ni(CN)2 core-shell heterostructure derived from Hofmann-type MOF as an efficient and durable high-performance noble metal-free electrocatalyst for hydrazine oxidation reaction (HzOR) in alkaline media. The sluggish oxygen evolution reaction was replaced with a more thermodynamically favourable HzOR, enabling energy-saving electrochemical hydrogen production with 2D NiCoMoS@Ni(CN)2 acting as a bifunctional electrocatalyst for anodic HzOR and cathodic hydrogen generation. Operating at room temperature, the two-electrode electrolyzer delivers 100 mA cm−2 from a cell voltage of just 257 mV, with strong long-term electrochemical durability and nearly 100% Faradaic efficiency for hydrogen evolution in 1.0 M KOH aqueous solution with 0.5 M hydrazine. The density functional theory (DFT) was employed to investigate the origin of catalytic performance and showed that high vacancy creation within the heterointerface endowed NiCoMoS@Ni(CN)2 with favourable functionalities for excellent catalytic performance.

Structural Modulation of Covalent Organic Frameworks for Efficient Hydrogen Peroxide Electrocatalysis.

The electrochemical production of hydrogen peroxide (H2O2) using metal-free catalysts has emerged as a viable and sustainable alternative to the conventional anthraquinone process. However, the precise architectural design of these electrocatalysts poses a significant challenge, requiring intricate structural engineering to optimize electron transfer during the oxygen reduction reaction (ORR). Herein, we introduce a novel design of covalent organic frameworks (COFs) that effectively shift the ORR from a four-electron to a more advantageous two-electron pathway. Notably, the JUC-660 COF, with strategically charge-modified benzyl moieties, achieved a continuous high H2O2 yield of over 1200 mmol g-1 h-1 for an impressive duration of over 85 hours in a flow cell setting, marking it as one of the most efficient metal-free and non-pyrolyzed H2O2 electrocatalysts reported to date. Theoretical computations alongside in situ infrared spectroscopy indicate that JUC-660 markedly diminishes the adsorption of the OOH* intermediate, thereby steering the ORR towards the desired pathway. Furthermore, the versatility of JUC-660 was demonstrated through its application in the electro-Fenton reaction, where it efficiently and rapidly removed aqueous contaminants. This work delineates a pioneering approach to altering the ORR pathway, ultimately paving the way for the development of highly effective metal-free H2O2 electrocatalysts.

In-situ construction of ionic liquid salt-derived graphene-like dual-heteroatoms doping engineering as efficient metal-free electrocatalyst for oxygen reduction reaction

Metal-free heteroatom-doped carbon catalysts can effectively eliminate the degradation and pollution problems caused by metal dissolution. However, single heteroatom doping often restricts the regulation of geometric and electronic structures for oxygen reduction reaction (ORR) electrocatalysts. Herein, a dual atomic doping engineering to optimize the electronic structure and local coordination environment of ionic liquid salt-derived graphene-like host material as an efficient metal-free electrocatalyst for ORR. The resultant PNG catalyst with a typical nanosheets morphology with a high specific surface area and unique hierarchical porous structure. Benefiting from the uniform doping of P, N heteroatoms, graphene-like structure, optimized electronic structure and coordination environment, thus-prepared PNG-2 exhibits outstanding ORR activity, which the onset potential and half-potential are negatively shifted by around 70 mV and 46 mV, respectively, as compared to the commercial Pt/C (20 wt.%) for ORR. Furthermore, the PNG-2 exhibits the higher diffusion limiting current density, superior long-term stability as well as excellent resistance to methanol oxidation than Pt/C. Experimental studies and density functional theory (DFT) calculations reveal that the enhanced chemisorption of oxygen species (*OOH, *O and *OH) onto the P and N sites of the PNG catalysts can effectively accelerate the charge transfer kinetics and promote a favorable ORR performance.

Synergistic enhancement of Zn-air battery performance via integration of Ni-doped cobalt sulfide nanoparticles within N, S-doped carbon matrix

Exploring precious metal-free bifunctional electrocatalysts for both the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) is essential for the practical application of rechargeable Zn-air battery (ZAB). Herein, Ni-doped Co9S8 nanoparticles embedded in a defect-rich N, S co-doped carbon matrix (d-NixCo9-xS8@NSC) are synthesized via a facile pyrolysis and acid treatment process. The introduction of abundant defects in both the carbon matrix and metal sulfide provides numerous active sites and significantly enhances the electrocatalytic performances for both the ORR and OER. d-NixCo9-xS8@NSC exhibits a superior half-wave potential of 0.841 V vs. RHE for the ORR and delivers a low overpotential of 0.329 V at 10 mA cm−2 for the OER. Additionally, Zn-air secondary battery using d-NixCo9-xS8@NSC as the air cathode displays a higher specific capacity of 734 mAh gZn−1 and a peak power density of 148.03 mW cm−2 compared to those of state-of-the-art Pt/C-RuO2 (673 mAh gZn−1 and 136.9 mW cm−2, respectively). These findings underscore the potential of d-NixCo9-xS8@NSC as a high-performance electrocatalyst for secondary ZABs, offering new perspectives on the design of efficient noble metal-free electrocatalysts for future energy storage and conversion applications.

Mesoporous carbon-doped boron nitrides for cathodic and anodic hydrogen peroxide electrosynthesis

Mesoporous carbon-doped hexagonal boron nitrides (C-doped BN) with high surface area were prepared by annealing organic resin polymer/silica in NaBH4 and NaNH2 inorganic salts, which were found to be efficient metal-free bifunctional electrocatalyst for both 2e− ORR and 2e− WOR. It could efficiently catalyze 2e− ORR to H2O2 in 2 M KHCO3 (1650 mmol g−1 h−1) with Faraday efficiency of 93–98 % in half reaction, while it was very active for 2e− WOR to generate H2O2 in 2 M KHCO3 with 551 mmol g−1 h−1 H2O2 production rate in half reaction. When pairing them in one H-type cell, H2O2 solution could be totally produced over C-doped BN in both anode and cathode cells. The better electron conductivity from sharper band gap caused by carbon doping and higher surface area of 304 m2 g−1 contributed to its efficient electrocatalytic activity. The C-doped BN served an effective bifunctional electrocatalyst for 2e− ORR and 2e− WOR.

Metal Doping Regulates Electrocatalysts Restructuring During Oxygen Evolution Reaction.

High-efficiency and low-cost catalysts for oxygen evolution reaction (OER) are critical for electrochemical water splitting to generate hydrogen, which is a clean fuel for sustainable energy conversion and storage. Among the emerging OER catalysts, transition metal dichalcogenides have exhibited superior activity compared to commercial standards such as RuO2, but inferior stability due to uncontrolled restructuring with OER. In this study, we create bimetallic sulfide catalysts by adapting the atomic ratio of Ni and Co in CoxNi1-xSy electrocatalysts to investigate the intricate restructuring processes. Surface-sensitive X-ray photoelectron spectroscopy and bulk-sensitive X-ray absorption spectroscopy confirmed the favorable restructuring of transition metal sulfide material following OER processes. Our results indicate that a small amount of Ni substitution can reshape the Co local electronic structure, which regulates the restructuring process to optimize the balance between OER activity and stability. This work represents a significant advancement in the development of efficient and noble metal-free OER electrocatalysts through a doping-regulated restructuring approach.

Metal-free N, B, F ternary-doped carbon electrocatalyst for boosting the oxygen reduction reaction and high-performance zinc–air battery

Developing efficient metal-free carbon-based electrocatalysts for the oxygen reduction reaction (ORR) is significant and challenging to reduce the cost of fuel cells and metal–air batteries for large-scale applications. Herein, a novel metal-free N, B, F ternary-doped carbon electrocatalyst (FBNCΔ(1:6)-950) exhibited an excellent ORR performance with half-wave potential of 0.858 V vs. reversible hydrogen electrode (RHE) via an almost exclusively four-electron transfer pathway in 0.1 M KOH, even better than the commercial Pt/C (20 %). Moreover, the FBNCΔ(1:6)-950-based zinc–air battery (ZAB) shown an excellent power density of 147 mW·cm−2 and long-term stability of 100 h. The FBNCΔ(1:6)-950 was constructed via pyrolyzing zeolite imidazole framework (ZIF-8) precursor containing BF4– at 950 °C under N2 to volatilize the Zn. According to the structural characterization and theoretical calculations, B and F from BF4– not only increased the number of active sites of pyridine-N by etching intact carbon matrix, but also co-modified part of pyridine-N to further optimize the electronic structure and reduce the adsorption energy of *OH, both of which together result in the excellent performance of FBNCΔ(1:6)-950. This work provides a fresh perspective on the advancement of highly active metal-free carbon-based electrocatalysts for the ORR and ZAB.

Pyridinic N and semi-ionic F Co-functionalized biochar nanofibers as efficient metal-free electrocatalysts for oxygen reduction reaction

Pyridinic N and semi-ionic F Co-functionalized biochar nanofibers as efficient metal-free electrocatalysts for oxygen reduction reaction

Ordered mesoporous carbon with binary CoFe atomic species for highly efficient oxygen reduction electrocatalysis.

The exploration of powerful, efficient and precious metal-free electrocatalysts for facilitating the sluggish kinetics of the oxygen reduction reaction (ORR) is a crucial endeavor in the development and application of energy conversion and storage devices. Herein, we have rationally designed and synthesized bimetallic CoFe species consisting of CoFe nanoparticles and atomically dispersed dual atoms anchored on an ordered mesoporous carbon matrix (CoFe/NC) as highly efficient ORR electrocatalysts. The pyrolyzation temperature for CoFe/NC plays a vital role in regulating the morphology and composition of both the carbon matrix and CoFe species. The optimized CoFe/NC-750 exhibits a favorable ORR performance in 0.1 M KOH with a high half-wave potential (E1/2) of 0.87 V vs. RHE, excellent tolerance to methanol and remarkable durability (no obvious decrease in E1/2 value after 3000 cycles), all of which are superior to the performance of commercial Pt/C. Experimental measurements and density functional theory (DFT) calculations reveal that the improved ORR performance of CoFe/NC-750 is mainly attributed to the electronic structure of atomically dispersed Fe active sites modulated by the surrounding CoFe alloys and Co single atoms, which accelerates the dissociation and reduction of intermediate OH* species and promotes the ORR process.

Two-dimensional phosphorus carbides (β-PC) as highly efficient metal-free electrocatalysts for lithium-sulfur batteries: a first-principles study.

Li-S batteries are considered as the next-generation batteries due to their exceptional theoretical capacity. However, their practical application is hampered by the shuttling effects of lithium polysulfides (LiPSs) and the sluggish Li2S decomposition, particularly the slow conversion from Li2S2 to Li2S. Addressing these challenges, the quest for effective catalysts that can accelerate the conversion of LiPSs and enhance the performance of Li-S batteries is crucial. In this study, we explored the electrocatalytic activity of two-dimensional phosphorus carbides (β0-PC and β1-PC) in Li-S batteries based on first-principles calculations. Our findings reveal that these materials demonstrate optimal binding strengths (ranging from 1.09 to 1.83 eV) with long-chain LiPSs, effectively preventing them from dissolving into the electrolyte. Additionally, they show remarkable catalytic activity during the sulfur redox reaction (SRR), with ΔG being only 0.37 eV for β0-PC and 0.13 eV for β1-PC. The low energy barrier induced by β-PC enhances ion migration barrier and significantly expedites the charge/discharge cycles of Li-S batteries. Furthermore, we investigated the conversion dynamics of Li2S2 to Li2S, employing the computational lithium electrode (CLE) model. The excellent performance in these aspects underscores the potential of these materials as electrocatalysts for Li-S batteries, paving the way for advanced high-efficiency energy storage solutions.

N-doped defect-rich porous carbon nanosheets framework from renewable biomass as efficient metal-free bifunctional electrocatalysts for HER and OER application

In response to the demand for clean, renewable energy sources and storage technologies, innovative materials and combinations have been developed at reasonable prices as effective electrode materials. Current research and development of carbon-based metal-free catalysts have opened up new research areas for bifunctional electrocatalysts for overall water splitting. Herein, we developed N-self-doped defect-rich porous carbon nanosheets derived from platycladus orientalis tree-cone biomass for overall water splitting. The developed N-self-doped defect-rich porous carbon nanosheets have large surface areas (3369 m2/g), high pore volumes (2.1 cm3 g−1), and high electrical conductivities (12.69 S/cm). N-self-doped defect-rich porous carbon nanosheet framework was employed in water splitting as a dual function in hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). Electrodes fabricated from the KOH-II ABC nanosheets show excellent OER and HER performances in the 0.5 M H2SO4 solution. The current density of 10 mA cm−2 is reached at a low overpotential of 90 mV for OER and 188 mV for HER. In addition, KOH-II ABC nanosheets also show a remarkable performance on overall water splitting, which only required a cell voltage of 1.49 V to reach current densities of 10 mA cm−2 in 0.5 M H2SO4 solution. The presence of defects in the carbon nanosheets, higher specific surface area, excellent electrochemical active surface area and N doping effectively enhance the reaction kinetics for attaining efficient OER and HER performances. This facile approach to preparing biomass-derived N-doped defect-rich porous carbon materials empowers next-generation green fuel conversion technologies for carbon neutrality.

Microwave-Assisted Synthesis of Nitrogen-Doped Carbon Catalysts for Oxygen Reduction Reaction with Tunable Selectivity

The oxygen reduction reaction (ORR) is the core reaction in electrocatalysis systems such as fuel cells, metal-air batteries and hydrogen peroxide (H2O2) electro-generation. The ORR reaction mechanism has two possible pathways, namely, two-electron (2e−) or four-electron (4e−) processes that enable a reduction of oxygen into H2O2 or water (H2O), respectively. Both paths are useful where the former can provide on-site direct production of H2O2 and the latter is desired in fuel cells and batteries since it enables higher energy efficiency. Optimal ORR electrocatalyst should exhibit high activity, selectivity, stability, and low cost. Carbon materials modified with heteroatoms (e.g. nitrogen (N)) are considered potential alternatives for costly noble metal catalysts including Pt for ORR in fuel cells, and Au for the ORR to H2O2 (1,2). The typical synthesis procedure for the porous nitrogen-doped carbons (N–C) is based on the single or multiple pyrolysis steps of nitrogen-rich carbon precursor. The reactions required a pyrolysis step at the temperature range of 500-1200 °C and timing of one to tens of hours. Such processes showed a highly negative environmental impact due to high energy consumption. The production of 1 ton of activated carbon from lignocellulosic biomass feedstock requires 669.83 kWh (equivalent to an emission of 62.78 tons of CO2) (3). The synthesis of the N–C by microwave (MW) irradiation can reduce energy usage and ensure a more environmentally sustainable and economically viable approach. This procedure necessitates non-transparent materials to electromagnetic waves that can convert MW energy into heat and simultaneously enable the carbonization of the starting material.This work investigated the electrocatalytic activity towards ORR for N–C–MW catalysts derived from polyaniline (PANI) prepared in a one-step MW carbonization approach. PANI was selected due to two reasons: (i) N–C made by thermal pyrolysis of PANI showed improved electrocatalytic activity toward ORR where both the 4e− and the 2e− electron transfer pathways are feasible depending on the nature of active sides (4), (ii) PANI displayed good MW adsorption properties (5). The work aimed to identify the influence of the MW reaction condition on the resulting structure of the N–C–MW and the direction of the ORR. The N–C–MW samples were prepared under MW power of 450 and 800 W and time of 70, 140 and 210 s. The ORR activity of N–C–MW samples was investigated by cyclic voltammetry in the alkaline media (O2-saturated 0.1 M KOH). The experiment was performed in a three-electrode configuration composed of a rotating ring (Pt)–disk (glassy carbon) electrode (RRDE), a graphite rod as the counter electrode and a reversible hydrogen electrode (RHE) as the reference electrode. An influence of catalyst loading on disk electrode (0.05, 0.1 and 0.2 mg/cm2) was analyzed. All investigated MW reaction conditions resulted in the formation of porous disordered carbon structures with nitrogen and oxygen functionalities confirmed by X-ray photon-electron spectroscopy. The shorter time (70 s) and lower power (450 W) of MW treatment resulted in the formation of structures with a low carbonization rate and simultaneously a relatively poor catalytic activity for ORR (an onset potential of ∼0.65 V vs RHE). The samples carbonized under moderate (power of 450 W and 800 W, time of 140 s) and severe (power of 450 W, time of 210 s) reaction conditions showed higher selectivity to H2O2 or water H2O, respectively. The selectivity of 80 % to H2O2 was achieved for the N–C–MW-800W-140s sample at the potential of 0.6 V vs RHE at the catalyst loading of 0.05 mg/cm2. The results showcase the potential of MW carbonization in producing ORR electrocatalysts with diverse functionalization, leading to modified reaction selectivity that can be utilized in various electrocatalytic applications. Acknowledgments The research leading to these results was supported by the Johannes Amos Comenius Programme, European Structural and Investment Funds, project 'CHEMFELLS V‘ (No. CZ.02.01.01/00/22_010/0003004). References Yang, S. et al., Toward the decentralized electrochemical production of H2O2: A focus on the catalysis. ACS Catalysis, 2018.Bouleau, L. et al., Best practices for ORR performance evaluation of metal-free porous carbon electrocatalysts. Carbon, 2022.Wang, YX. et al., Quantifying environmental and economic impacts of highly porous activated carbon from lignocellulosic biomass for high-performance supercapacitors. Energies, 2022.Silva, R. et al., Efficient metal-free electrocatalysts for oxygen reduction: Polyaniline-derived N- and O-doped mesoporous carbons. Journal of the American Chemical Society, 2013.Oyharçabal, M. et al., Influence of the morphology of polyaniline on the microwave absorption properties of epoxy polyaniline composites. Composites Science and Technology, 2013. Figure 1

Computational evaluation of CO2 conversion into formic acid via a novel adsorption mechanism on metal-free B4C12

The electrochemical reduction of CO2 (CO2RR) to formic acid (HCOOH) is a promising approach to harness renewable energy for the production of value-added chemicals and contribute to carbon cycling. The search for cost-effective and efficient metal-free electrocatalysts is critical for realizing industrial applications. However, limited literature is available on this topic, primarily because the significant challenge of efficiently activating inert CO2 remains unresolved. In this study, we have designed and applied a novel boron carbide (B4C12) monolayered cage as an electrocatalyst for CO2RR to produce HCOOH. B4C12 exhibits exceptional electronic, dynamic, and thermodynamic stability. Through comprehensive density functional theory computations, we have observed that B4C12 rapidly and stably adsorbs CO2 in a unique η3(O, C, O)-CO2 configuration, resulting in excellent CO2RR activity with a low limiting potential (–0.38 V) and suppressed hydrogen evolution reaction. Our mechanistic investigations reveal that B4C12 donates electrons to facilitate the bending of CO2, anchoring it onto the curved surface effectively. Additionally, the C atom in the η3(O, C, O)-CO2 configuration attracts H+ + e− pairs through its active p electron, leading to the observed low limiting potential. This study not only successfully designs a novel class of metal-free electrocatalysts but also provides a promising strategy for advancing CO2RR research in the future.

Heterogeneous N-heterocyclic carbenes: Efficient and selective metal-free electrocatalysts for CO reduction to multi-carbon products

Electrochemical reduction of CO2 to valuable multi-carbon products is an important potential solution to environmental and energy crises caused by fossil fuel burning. As an effective way to address the drawbacks of direct CO2 reduction, the reduction of CO to multi-carbon products remains a challenge, specially lacking high-efficient, selective and low-cost metal-free catalysts. N-heterocyclic carbenes (NHCs) have been shown to be effective metal-free catalysts for converting CO2 to CO or C1-products, but the facile release of CO limits the further reduction to valuable multi-carbon fuels. In this study, using density functional theory calculations, we developed heterogeneous NHCs by incorporating NHCs into the graphene lattice and found that these NHCs could stably adsorb and effectively activate CO molecules, enabling the efficient conversion of CO into CH3OH, C2H4 and C2H5OH with low limiting potentials, i.e., –0.70, –0.45 and –0.36 V, respectively. These limiting potentials for C2-products are lower than those of most known metal-based or metal-free electrocatalysts. Moreover, competitive hydrogen evolution reaction can be effectively inhibited. The excellent catalytic performance is attributed to the charge transfer between NHCs and CO as well as the strong hybridization of C-2p orbitals of carbene carbon atoms in NHCs and carbon atoms in CO molecule. Our findings suggest that these heterogeneous NHCs exhibit high catalytic activity and selectivity for the conversion of CO to valuable C2-products. This study is the first report of NHC-based metal-free electrocatalysts for the conversion of CO to multi-carbon products, which will offer cost-effective opportunities for CO2 reduction.

Engineering S, N-doped carbon nanosheets derived from thiazolothiazole-based conjugated polymer for efficient electrocatalytic oxygen evolution and Zn-air battery

Electrochemical oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) by using metal-free electrocatalysts is an emerging research interest for clean energy due to its cost affordability and eco-friendliness. However, only a few metal-free electrocatalysts are reported to exhibit robust OER and ORR performances, although OER and ORR are very important in various energy technology like metal-air batteries, fuel cells, etc. Herein, we have developed a rigid thiazolo [5,4-d] thiazole-based organic conjugated polymer, P-TzTz, and its polymer-derived N and S-doped carbon nanosheets for metal-free electrocatalytic OER and ORR. The polymer possesses a unique two-dimensional nanosheet structure with a moderate surface area of 72.6 m2/g and a wide range of pore sizes. The synthesized P-TzTz displayed a reasonable electrocatalytic OER performance with excellent long-term stability. The OER performance was further enhanced by pyrolyzing the P-TzTz at 800 °C to prepare the N and S-doped carbon nanosheet, P-TzTz-CNS800. The elevated surface area (228 m2/g) with uniform mesopores, enhanced electrical conductivity of P-TzTz-CNS800, and the presence of N, and S as the dopants for improving active sites made the P-TzTz-CNS800 a promising OER/ORR electrocatalyst as it showed the OER overpotential of 347 mV@10 mA/cm2 current density with more than 45 h long-range durability and 98% Faradic efficiency of oxygen evolution. Finally, to utilize the good OER efficacy of P-TzTz-CNS800-based metal-free electrocatalyst, a rechargeable Zn-air battery was fabricated as a proof of concept by taking P-TzTz-CNS800 as the air cathode. The Zn-air battery revealed a constant open circuit potential of 1.44 V and high charging/discharging stability over 40 h with a minimal loss in round trip frequency. Thus, the report corroborates the promising potential of P-TzTz derived N and S-doped carbon nanosheets as an efficient metal-free electrocatalyst as an air cathode for Zn-air battery for clean energy conversion.

Facilitating two-electron oxygen reduction with pyrrolic nitrogen sites for electrochemical hydrogen peroxide production

Electrocatalytic hydrogen peroxide (H2O2) production via the two-electron oxygen reduction reaction is a promising alternative to the energy-intensive and high-pollution anthraquinone oxidation process. However, developing advanced electrocatalysts with high H2O2 yield, selectivity, and durability is still challenging, because of the limited quantity and easy passivation of active sites on typical metal-containing catalysts, especially for the state-of-the-art single-atom ones. To address this, we report a graphene/mesoporous carbon composite for high-rate and high-efficiency 2e− oxygen reduction catalysis. The coordination of pyrrolic-N sites -modulates the adsorption configuration of the *OOH species to provide a kinetically favorable pathway for H2O2 production. Consequently, the H2O2 yield approaches 30 mol g−1 h−1 with a Faradaic efficiency of 80% and excellent durability, yielding a high H2O2 concentration of 7.2 g L−1. This strategy of manipulating the adsorption configuration of reactants with multiple non-metal active sites provides a strategy to design efficient and durable metal-free electrocatalyst for 2e− oxygen reduction.

Holey MXene nanosheets intimately coupled with ultrathin Ni–Fe layered double hydroxides for boosted hydrogen and oxygen evolution reactions

Although Ni–Fe layered double hydroxides (LDH) are considered as efficient noble metal-free electrocatalysts for both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), their overall electrocatalytic performance still needs to be significantly enhanced to satisfy the requirements of practical water splitting systems. Herein, we demonstrate the reasonable design and controllable fabrication of holey Ti3C2Tx MXene nanosheets intimately coupled with ultrathin Ni–Fe LDHs (LDH/H–Ti3C2Tx) through a combined in situ oxidative etching and hydrothermal assembly strategy. Such a newly-developed nanoarchitecture with abundant in-plane holes not only creates a sophisticated three-dimensional (3D) ion diffusion model to shorten the diffusion path of reactants, but also exposes a large number of extra catalytically active sites as well as guarantees a high charge transfer rate, which enable to dramatically accelerate the electrochemical HER and OER kinetics. As a consequence, the resulting LDH/H–Ti3C2Tx catalyst affords exceptional HER and OER performance with low overpotentials, small Tafel plots and excellent cycling stability, far outperforming the bare Ni–Fe LDHs and Ti3C2Tx catalysts. This work is expected to open up a new avenue to the confined growth of active nanomaterials on holey MXene nanosheets and promote their applications in the energy-conversion and -storage fields.

High Density Single Fe Atoms on Mesoporous N-Doped Carbons: Noble Metal-Free Electrocatalysts for Oxygen Reduction Reaction in Acidic and Alkaline Media.

It remains a challenge to develop efficient noble metal-free electrocatalysts for the oxygen reduction reaction (ORR) in various renewable energy systems. Single atom catalysts have recently drawn great attention as promising candidates both due to their high activity and their utmost atom utilization for electrocatalytic ORR. Herein, the synthesis of an efficient ORR electrocatalyst that is composed of N-doped mesoporous carbon and a high density (4.05 wt%) of single Fe atoms via pyrolysis Fe-conjugated polymer is reported. Benefiting from the abundant atomic Fe-N4 sites on its conductive, mesoporous carbon structures, this material exhibits an excellent electrocatalytic activity for ORR, with positive onset potentials of 0.93 and 0.98V in acidic and alkaline media, respectively. Its electrocatalytic performance for ORR is also comparable to that of Pt/C (20 wt%) in both media. Furthermore, it electrocatalyzes the reaction almost fully to H2 O (or barely to H2 O2 ). Additionally, it is durable and tolerates the methanol crossover reaction well. Furthermore, a proton exchange membrane fuel cell and a zinc-air battery assembled using it on their cathodedeliver high maximum power densities (320 and 91mW cm-2 , respectively). Density functional theory calculation reveals that the material's decent electrocatalytic performance for ORR is due to its atomically dispersed Fe-N4 sites.